Selectivity Switching of CO2Hydrogenation from HCOOH to CO with an in Situ Formed Ru-Li Complex

an In Situ Formed Ru −Li Complex

Research Article

Selectivity Switching of CO Hydrogenation from HCOOH to CO with

Qiongyao Chen, Chaoren Shen, Gangli Zhu,* Xuehua Zhang, Chun-Lin Lv,* Bo Zeng, Sen Wang,

Junfen Li, Weibin Fan, and Lin He*

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sı Supporting Information

ABSTRACT: Herein, we report the role of alkali halide salt in

regulating the pathway of CO hydrogenation in the presence of

Shvo’s complex. Particularly, the collaboration of Shvo’s complex

with LiCl exhibited as a highly eﬃcient catalyst for CO₂

hydrogenation to CO instead of the kinetically favorable product

HCOOH under mild conditions. The reaction can be initiated at 45

°C with CO as the dominant product, and the rate of CO formation

was almost 80 times to that in the absence of LiCl at 60 °C. Under

optimized conditions, the TON_C_Ocould reach 1555 at 160 °C,

much higher than the reported results of the most eﬃcient Ru-based

homogeneous catalyst. Density functional theory calculations

demonstrated that the cooperation of the alkali cation and chloride

anion contributed to reducing the energy barrier of CO activation

to form the key Ru−CO H intermediate. An in situ formed mixed

Ru−Li complex (5) has been characterized by X-ray crystallography, highlighting the indispensability of electrostatic interactions

between LiCl and Shvo’s complex for enhanced reactivity and altered selectivity.

KEYWORDS: alkali metal salts, CO hydrogenation, promoter eﬀect, selectivity switch, Ru−Li complex.

. INTRODUCTION

Scheme 1. Selectivity Switching of CO Hydrogenation

Hydrogenation of CO is a process with several possible

channels, leading to various products, including HCOOH,

CO, MeOH, and CH . Among these, direct hydrogenation

of CO to CO, the reverse water gas shift reaction (RWGS),

oﬀers a promising approach to access the sustainable source for

synthesis gas. Despite its utility, the procedure often demands

harsh conditions (>160 °C in most cases) and suﬀers from

competition with other reaction pathways. Moreover, under

mild conditions, CO formation is kinetically disfavored

compared with HCOOH formation. This situation becomes

more signiﬁcant to homogeneous catalysts with ligands bearing

O−H/N−H groups as the hydrogen-bonding interaction

between the functional groups and the oxygen of CO is

60 °C). Under the optimized conditions, the TONCO could

reach 1555 at 160 °C, much higher than that of state-of-the-art

Ru-based homogeneous catalytic systems. Density functional

beneﬁcial to generate the formate (MO CH) intermediate.

Thus, the prediction regarding the chemoselectivity of CO₂

hydrogenation catalyzed by hydroxycyclopentadienyl metal

complexes (including Shvo’s catalyst 1) gives HCOOH instead

theory (DFT) calculations validated the contribution of Li

of CO as the default product, although experimentally, these

Received: April 26, 2021

Revised: June 23, 2021

Published: July 13, 2021

types of catalysts for CO hydrogenation were unexplored

prior to this report.

In the present work (Scheme 1), the capability of Shvo’s

catalyst for hydrogenating CO to HCOOH was conﬁrmed.

More intriguingly, adding LiCl can switch the selectivity of the

product toward CO even at extremely low temperatures (45−

2021 American Chemical Society

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Research Article

and Cl⁻in reducing the formation energy of the MCO H

V_C_O_%₌Ai × 2% GC b

intermediate for RWGS. A Ru−Li complex (5) formed in situ

has been characterized by X-ray crystallography, revealing the

substitution of the acidic proton on the hydroxycyclopenta-

dienyl ligand and carbonyl ligand on the Ru center respectively

A_S

(2)

^R^T^×ⁿRu

^T^O^NCO

^×^VCO

−

(3)

with Li and Cl . This is an unusual example supported with

crystallographic evidence that clariﬁes the coexistence of the

alkali cation and chloride anion in prompting the catalytic

reactivity and altering the reaction pathway.

where A is the peak area of CO, A is the peak area of the

standard gas with V_C_O% equal to 0.5006% or 2%, V_C_O% ≤ 1

vol % [GC a], V_C_O% ≥ 1−3 vol % [GC b], P is the total

pressure of the Parr autoclave (Pa), V is the total volume of the

. EXPERIMENTAL DETAILS

.1. Catalyst Synthesis. For the synthesis of Shvo’s

Parr autoclave (m ), T = 298 (K), R = 8.314 J/(mol·K), and

n_R_uis the mole of the metal (mol).

2.3. In Situ Formation of Intermediate 5 under the

catalyst, complexes 2, 3, and 4 were synthesized according to

the previous reports. Detailed procedures are in Section 2 of

the Supporting Information.

Optimal Conditions. The 100 mL Parr autoclave was

charged with Shvo’s catalyst (135 mg, 0.125 mmol), LiCl

0.5 mmol), NMP (1.5 mL), and a magnetic stirring bar. At

room temperature, the autoclave was ﬂushed with CO three

(

.1.1. Synthesis of Complex 5. A 50 mL autoclave was

charged with Shvo’s catalyst (271 mg, 0.25 mmol) or complex

(271 mg, 0.5 mmol), LiCl (43 mg, 1 mmol), N-methyl-2-

times. Then, CO was charged up to 3 MPa, followed by

charging H to obtain a total pressure of 6 MPa. The reaction

pyrrolidone (NMP, 2 mL), and a magnetic stirring bar. At

mixture was heated at 120 °C for 1 h. After cooling to room

temperature, the residue gas was slowly released. CH Cl (ca.

room temperature, the autoclave was ﬂushed with N three

times. Then, the pressure of N was charged up to 1 MPa. The

−3 mL) was added into the reaction solution, and the

reaction mixture was heated at 120 °C for 5 h. Afterward, the

autoclave was cooled to room temperature, and the residue gas

was slowly released. 2−3 mL of CH Cl was added to the

reaction mixture was ﬁltered oﬀ. Single crystals were cultivated

by the liquid−liquid diﬀusion technique via layering the

CH Cl solution with hexane. After 3 days, light-yellow crystals

reaction solution, and the reaction mixture was ﬁltered oﬀ.

Then, hexane was added into the ﬁltrate, and the resulting

pale-yellow powder 5 was ﬁltered oﬀ (261 mg, 83%). Single

crystals were cultivated by the liquid−liquid diﬀusion

were obtained. The results of X-ray crystallographic character-

ization show that complex 5 also exists under the reaction

conditions.

2.4. Procedures for Investigating the Active Ru−H

Species. 2.4.1. Evidence for the Interaction between LiCl

and Shvo’s Catalyst. After reaction in anhydrous THF under

technique via layering the CH Cl solution with hexane. H

NMR (CDCl , 400 MHz): δ 7.40−7.42 (m, 4H), 7.19−7.21

(

m, 6H), 7.11 (m, 2H), 7.0−7.04 (m, 4H), 6.90−6.93 (m,

MPa of H at 120 °C for 10 h, Shvo’s catalyst was

H), 3.36 (t, J = 7.1 Hz, 2H), 2.81 (s, 3H), 2.33 (t, J = 8.1 Hz,

transformed to the mixture of Ru−H complexes. The H NMR

spectra of this mixture containing Ru−H complexes displayed

two resonance signals at −9.87 and −10.13 ppm (the

procedure was identical to the procedure of preparing complex

H), 1.95−2.03 (m, 2H). C NMR (CD OD, 100.6 MHz): δ

01.00, 176.34, 133.50, 132.44, 132.01, 131.43, 130.81, 127.46,

27.02, 126.97, 125.92, 101.16, 82.57, 49.46, 30.31, 28.42,

7.18. HRMS-ESI (m/z): [M − H] calcd for

−

except changing the temperature to 120 °C). The resonance

−

C H ClO Ru , 577.0155; found, 557.0173.

signal at −9.87 ppm can be attributed to complex 2.

To investigate the interaction between LiCl and Shvo’s

catalyst, the following operation was performed in a glovebox

.2. General Procedures for the CO Hydrogenation

Process. The following procedure for CO hydrogenation

reactions can be considered representative. A 100 mL Parr

autoclave was charged with the Ru-based catalyst (0.05 mmol),

the additive (0.1 mmol), the solvent (1 mL), and a magnetic

stirring bar. At room temperature, the autoclave was ﬂushed

with N gas protection. An NMR tube was charged with the

mixture of Ru−H complexes (20 mg) and anhydrous CDCl

600 μL). Then, LiCl (3 mg) dissolving in NMP (200 μL) was

subjected to the NMR tube. The reaction between complex 2

and LiCl proceeds fast enough under ambient conditions. This

(

with carbon dioxide three times. Then, CO was charged up to

MPa, followed by charging H to obtain a total pressure of 6

solution was characterized by H NMR as quickly as possible.

MPa. The reaction mixture was heated at 120 °C for 10 h.

Afterward, the autoclave was cooled to room temperature. Gas

products were collected by gas sampling bags after reaction

and were analyzed by gas chromatography equipped with a

thermal conductivity detector (TCD) and ﬂame ionization

detector (FID). TON_C_Oof gaseous products was determined

based on the gas chromatography (GC) analysis results. Gas

products were analyzed using FID with a methanizer or TCD

2.4.2. Investigating the Evolution of Complex 5 under 6

MPa H and under Optimized Reaction Conditions. All the

following operations were conducted in a glovebox with N gas

protection. A 50 mL autoclave was charged with Ru complex 5

174 mg, 0.1 mmol), NMP (2 mL), and a magnetic stirring

bar. At room temperature, the autoclave was ﬂushed with H₂

(

three times. Then, the pressure of H was charged up to 6

MPa. The reaction mixture was heated at 120 °C for 1 h. After

cooling the autoclave to room temperature, the residual gas

was slowly released. Then, the autoclave was transferred into a

for CO. The liquid product (HCOOH) was determined by H

NMR with N,N-dimethylformamide (DMF) as an internal

standard. The concentration of gaseous products was

quantiﬁed by the integral area ratio of the reduction products

to the standard gas. TON_C_Oof gaseous products were

calculated by the following equations:

glovebox with N gas protection. 100 μL of NMP solution of

the reaction mixture was subjected to an NMR tube charged

with 600 μL of CDCl for H NMR analysis. The above-

mentioned experimental procedure was repeated, except that 3

MPa CO together with 3 MPa H instead of 6 MPa H was

V_C_O% = _A× 0.5006% GC a

charged to conﬁrm the Ru−H species under reaction

conditions.

(1)

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.5. Computational Methods. All the calculations

was switched from HCOOH to CO (entries 2−5). Among the

presented in this work were carried out with the Gaussian

6 software package. The structures of reactants, inter-

salts tested, LiCl performed best in the low-temperature

hydrogenation of CO to CO. With the addition of 2 equiv

mediates, and products as well as transition states were

optimized using the B3LYP hybrid-GGA functional, in

LiCl, the selectivity toward CO increased from 5 to 95%.

Correspondingly, the RWGS activity was elevated by almost 2

orders of magnitude compared to the system without adding

the salt (480 vs 6 μmol). Of alkali halide salts other than LiF

and LiI, LiBr also manifested a signiﬁcant positive eﬀect on

facilitating CO generation (entries 6−8). The observed subtle

promoting eﬀect of halides is probably attributed to the

solubility of lithium halide and the coordination of the halide

anion to Ru. RWGS can be initiated at 45 °C, giving CO as the

main product, indicating the crucial role of LiCl (entry 9). The

observed activity was compared with those of the reported

catalysts. At 100 °C, the turnover number of CO (TON_C_O) on

Shvo’s catalyst was more than 5 times that of either Ru (CO)

combination with the LANL2DZ basis set for Ru atoms

and the 6-31G(d, p) basis set for rest atoms (BS1). Vibrational

frequencies of each stationary structure were analyzed at the

same level of theory to characterize the nature of the stationary

points as local minima and give the thermal correction to

Gibbs free energy. The minimum-energy path was obtained

using intrinsic reaction coordinate calculations to conﬁrm the

connection of each transition state with the designated

equilibrium species. In addition, the implicit solvation of

N,N-dimethylacetamide has also been considered. Single-point

energy calculations have been performed using the polarized

continuum model with the SMD-Coulomb atomic radii for

the united atom topological model at the B3LYP level based

or [RuCl (CO) ] (entries S4−S6 in Table S1). Even at a 20

3 2

°C lower temperature, the activity of Shvo’s catalyst was

on each optimized geometry, with the SDD basis set for Ru

atoms and the 6-311+G(d,p) basis set for rest atoms, denoted

as B3LYP-SCRF(SMD)/BS2.

approximately twice that of [PPN][RuCl (CO) ], which was

claimed as the most eﬃcient homogeneous catalyst for low-

temperature RWGS (TON_C_O: 89 at 120 °C vs 43 at 140 °C;

entry S16).

The reaction conditions were brieﬂy screened, and the

TON_C_Oincreased with the increase of reaction temperature

from 45 to 120 °C (entries 2 and 9−12). The eﬀect from the

stoichiometry of the alkali salt on the reaction was evaluated.

The optimal ratio of LiCl/Ru at 60 °C is ca. 2 (Figure S1).

Increasing pressure leads to a higher gas solubility and reaction

rate, which results in higher e ﬃ ciency of CO production

. RESULTS AND DISCUSSION

The investigation started from evaluating the catalytic

performance under CO (3 MPa) and H (3 MPa) at 60 °C

for 10 h (Table 1). The activity of Shvo’s catalyst for CO₂

hydrogenation was conﬁrmed (entry 1). By adding diﬀerent

alkali chloride salts, the major product of CO hydrogenation

(

entries 12 and 14 and Figure S2a). The concentration of

Table 1. Inﬂuence of Alkali Halides on the Selectivity of

Shvo’s catalyst is the other major concern (entries 15 and 16).

By decreasing the concentration of the catalyst to 0.001 mol/L,

^t^h^e^v^a^l^u^e^o^f^T^O^NCO could attain 290, while the selectivity

toward CO was sustained above 99%. Amide solvents, such as

NMP, N-ethyl-2-pyrrolidone, DMF, and N ,N -dimethylaceta-

mide, were superior to other solvents (Figure S2b). When

further elevating the reaction temperature to 140 or 160 °C

but reducing the concentration of Shvo’s catalyst (0.001 mol/

L), this set of catalyst−promoter combinations still exhibited

remarkable catalytic performance with high CO selectivity

CO Hydrogenation

Shvo’s catalyst

CO + H ⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯ →⎯ CO + H O

temp.

entry

salt

(°C)

n (μmol)

TON

sel. (%)

FA CO FA

6.5

486.9

204.5

156.7

221.0

28.8

none

LiCl

NaCl

KCl

CsCl

LiF

123.9

40.7

71.9

67.3

54.5

∼0

>99

(

entries 17 and 18). The value of TON_C_Ocould reach 1555

when the reaction temperature was increased to 160 °C.

The signiﬁcant activity enhancement of Shvo’s catalyst with

55.0

−

the addition of LiCl led us to survey the role of Li and Cl

ions. To assess the eﬀect from Li , complex 3 possessing the

Cl ligand was prepared and applied into the CO₂

hydrogenation (Figure 1). It was almost inactive with a

^T ^O ^N CO of only 4. Adding LiCl dramatically increased the

LiBr

LiI

254.7

7.2

132.6

205.0

64.0

∼0

−

LiCl

167.0

1271.3

3385.5

4442.4

N.D.

4928.8

2886.3

579.1

992.7

3110.2

52.9

100

120

140

160

trace

N.D.

trace

N.D.

>99

115

290

496

1555

Reaction conditions: 0.025 mmol Shvo’s catalyst, 0.1 mmol salt, 1

mL of NMP, 3 MPa CO and 3 MPa H , 10 h. n is determined

HCOOH

by H NMR with DMF as an internal standard. Without Shvo’s

catalyst. 4 MPa CO and 4 MPa H . 0.0125 mmol Shvo’s catalyst

Figure 1. Indispensability of LiCl and the OH group of the ligand to

and 0.05 mmol salt. 0.001 mmol Shvo’s catalyst and 0.004 mmol salt.

RWGS activity ( reactions with 0.05 mmol Ru, 1 mL of NMP, 3 MPa

.001 mmol Shvo’s catalyst. N.D. = not detected. FA = formic acid.

CO , 3 MPa H , 120 °C, 10 h. All results represent the average values

All results represent the average values for the results of three runs.

of the results for three runs).

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Figure 2. Free-energy proﬁle with considering implicit solvation for the diﬀerent manners of inserting CO into the Ru−H bond: (a) forming Ru−

CO H and Ru−formate in the absence of LiCl; (b) forming Ru−CO H in the presence of LiCl.

activity. This contrast revealed the critical role of Li in the

Consequently, in the absence of LiCl, HCOOH would be the

dominant product (Table 1, entry 1).

−

conversion of CO to CO. The Cl anion was essential to the

catalytic system, with only deﬁcient performance in facilitating

In contrast, the presence of LiCl drastically mitigated the

−

CO generation being found when Cl was replaced with AcO ,

resistance of Ru−CO H intermediate IM3 in path III heading

−

2−

NO , HO , or CO (Figure S4). The results also indicated

to CO, which was aﬃrmed by the signiﬁcantly diminished

energy barrier (Figure 2b). Via substituting the acidic proton

on the hydroxycyclopentadienyl ligand and a carbonyl ligated

that the eﬀect of the alkali metal salt was unrelated to its

alkaline nature. The acidic proton on the hydroxycyclopenta-

dienyl ligand was suspected to be related to the high RWGS

activity. Accordingly, by replacing the hydroxyl group with the

−

to the Ru center respectively with Li and Cl , Shvo’s catalyst

was transformed to the anionic active species S3. The

−

coordination with Cl instead of CO enhances the

phenyl substituent, complex 4 was synthesized for comparing

with Shov’s catalyst. As expected, the TON_C_Odropped from

nucleophilicity of Ru-hydride, which changes to the manner

of CO insertion into Ru−H (the detailed natural charge

9 to 11 even in the presence of LiCl when applying complex 4

analysis of S1, S3, TS1, and TS3; see Figure S8 ). These

as the catalyst. These patterns suggested the indispensability of

−

outcomes showed that the presence of the LiCl additive indeed

both Li and Cl ions to the activity of Shvo’s catalyst for

RWGS and further demonstrated the collaboration between

Shvo’s catalyst and the LiCl additive.

imposes eﬀects on the chemoselectivity of CO hydrogenation

by altering the mechanism.

A plausible mechanism based on these experimental and

theoretical studies is proposed (Scheme 2). Initially, complex 2

is in situ generated via the splitting of Shvo’s catalyst in the

By the tool of DFT-based computation, the cooperation of

Shvo’s catalyst with the LiCl additive for switching the

selectivity of CO hydrogenation was elucidated by comparing

presence of H . Afterward, Ru−H complex S3 is aﬀorded via

the scenarios with and without LiCl (Figure 2). The activation

of CO and the heterolytic cleavage of H are the key steps

the substitution of the carbonyl ligand with LiCl. Via TS3, the

insertion of CO into the Ru−H bond aﬀords IM3. After CO

during the hydrogenation of CO . Revealed by DFT results

activation, the dehydration of IM3 gives intermediate 5.

Through the dissociation of carbonyl, the undercoordinated

intermediate 6 is formed. Finally, via the heterolytic splitting of

Figure S6 ), the relative energy barrier of H splitting (15.6

kcal/mol) was signiﬁcantly lower than that of CO activation

(

55.5 kcal/mol), indicating that the CO activation should be

H on intermediate 6 and the exchanging between the proton

the rate-determining step. This energy pattern is also

of the hydroxy group and Li (6 → 7 → 8 → S3), the active

8b,18

consistent with the previous reports.

Concerning the

species is regenerated.

CO activation, the distinct manner for inserting CO into the

To validate the proposed mechanism, we attempted to

obtain intermediate 5 and investigate its reactivity of RWGS.

Fortunately, intermediate 5 was air-stable enough to be

prepared via the reaction of either Shvo’s catalyst or complex

with LiCl under a N₂atmosphere (for the detailed

procedure, see Section 2.1). Intermediate 5 in the NMP-

Ru−H bond results in two plausible paths. One is via aﬀording

the Ru−formate intermediate, which would lead the selectivity

toward HCOOH through an “outer-sphere” hydrogenation

0a,19

mechanism.

The other is via generating the Ru−COOH

intermediate, which further undergoes protonation and

dehydration to aﬀord CO. The computational outcomes

solvated dimeric form was characterized by X-ray crystallog-

show that in the absence of LiCl, generating HCOOH starting

raphy (Figures 3a and S10). More importantly, under the

from the reaction between charge-neutral active species S1

optimal conditions for the CO hydrogenation to CO with a

and CO via path II through Ru−formate intermediate IM2

higher loading of Shvo’s catalyst, intermediate 5 was detected

and isolated (for the detailed procedure, see Section 2.3). At

the same time, we also observed the other molecular ion peak

with an m/z of 540.0210 (Figure 3c), which can be attributed

to the anionic moiety of intermediate 6 formed via one

carbonyl ligand dissociating from intermediate 5. To verify the

was much more favorable than producing CO along path I

through Ru−CO H intermediate IM1 (23.9 and 55.5 kcal/

mol, respectively, Figures 2a and S7). The priority of yielding

IM2 can be attributed to the H-bonding interaction between

10a

the hydroxyl group of the ligand and the oxygen of CO₂.

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we further attempted to observe the air-unstable active Ru −H

Research Article

Scheme 2. Plausible Mechanism for LiCl-Assisted CO₂

Hydrogenation to CO

species 8 or S3 by ex situ H NMR (Figure 3d; for details, see

Section 2.4). The resonance signal at −9.87 ppm can be

assigned to the hydride of complex 2. After the reaction

under a 6 MPa H atmosphere at 120 °C, a resonance signal

aroused at −10.13 ppm (inset I) was suggested as the Ru−H

species aﬀorded from complex 2 releasing one carbonyl ligand.

Afterward, adding LiCl into the mixture obtained from the

reaction with 6 MPa H led to the arising of two resonance

signals at −9.92 and −10.20 ppm (inset II). The chemical

shifts of these two peaks were identical to the resonance signals

observed when treating complex 5 with 6 MPa H (inset III).

These patterns suggest that the resonance signal at −9.92 ppm

can probably be attributed to the hydride of 8 or S3, which was

formed via complex 5 releasing the carbonyl ligand and then

splitting H . The presence of the resonance signal at −9.92

ppm was also observed in the reaction mixture obtained from

the 1 h reaction under the optimal conditions with 3 MPa H₂

and 3 MPa CO (inset IV). These results support the proposed

plausible mechanism illustrated in Scheme 2.

4. CONCLUSIONS

In summary, the hydrogenation of CO to CO by Shvo’s

catalyst can be initiated at a temperature as low as 45 °C with

the aid of LiCl, and the rate of CO generation was enhanced to

about 80 times at 60 °C. By the in situ formed Ru−Li complex,

the chemoselectivity at low temperatures can be switched from

HCOOH to CO. Our mechanistic investigation by theoretical

computations, control experiments, and the characterization of

crystallography and NMR uncovered the collaboration

between Shvo’s catalyst and alkali halide salts during the

activity and chemoselectivity of complex 5 in the CO₂

hydrogenation, complex 5 was subjected to the reaction

without adding LiCl. It exhibited almost the same catalytic

eﬀect as shown by employing the combination of Shvo’s

catalyst and LiCl (Figure 3b). On the basis of these ﬁndings,

CO hydrogenation and elucidated the role of alkali metal salts

Figure 3. Evidence supporting the proposed plausible mechanism. (a) ORTEP diagram of intermediate 5 showing thermal ellipsoids at the level of

0% probability (H atoms and the moiety of the NMP solvent are omitted for clarity). (b) Validating the activity of 5 for CO hydrogenation to

CO. Reaction conditions refer to the footnote in Figure 1. (c) Evidence provided by HRMS indicating the presence of intermediates 5 and 6; (d)

H NMR evidence for the presence of hydride species. Inset I: Shvo’s catalyst was treated under 6 MPa H at 120 °C for 10 h; inset II: LiCl and

NMP were added into the mixture isolated from inset I; inset III: complex 5 under 6 MPa H at 120 °C for 1 h; inset IV: complex 5 under 3 MPa

H and 3 MPa CO at 120 °C for 1 h.

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ACS Catal. 2021, 11, 9390−9396

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https://pubs.acs.org/doi/10.1021/acscatal.1c01874.

Research Article

in switching the chemoselectivity from generating HCOOH to

CO.

Conversion, Institute of Coal Chemistry, Chinese Academy of

Sciences, Taiyuan 030001, China

Weibin Fan − State Key Laboratory of Coal Conversion,

Institute of Coal Chemistry, Chinese Academy of Sciences,

Taiyuan 030001, China; orcid.org/0000-0001-7362-

ASSOCIATED CONTENT

sı Supporting Information

The Supporting Information is available free of charge at

■

0348

Complete contact information is available at:

https://pubs.acs.org/10.1021/acscatal.1c01874

General information, synthesis of catalysts, additional

data of CO hydrogenation, and XYZ coordinates for the

critical transition states on DFT calculations (PDF)

Author Contributions

The manuscript was written through contributions of all

authors. All authors have given approval to the ﬁnal version of

the manuscript. Q.C. and C.S. contributed equally.

Crystallography data of compounds (CIF)

AUTHOR INFORMATION

Corresponding Authors

Gangli Zhu − State Key Laboratory for Oxo Synthesis and

Selective Oxidation (OSSO), Suzhou Research Institute of

LICP, Lanzhou Institute of Chemical Physics (LICP),

Chinese Academy of Sciences (CAS), Lanzhou 730000,

China; University of Chinese Academy of Sciences, Beijing

■

Funding

The Dalian National Laboratory for Clean Energy (DNL)

Cooperation Fund, the CAS (DNL201919), the National

Natural Science Foundation of China (nos. 21802151,

21972152, and 21802152), the Natural Science Foundation

of the Jiangsu Higher Education Institutions of China

(BK20180249), the Key Research Program of Frontier

Sciences of CAS (QYZDJ-SSW-SLH051), and the Youth

Innovation Promotion Association of CAS (2018453) are

acknowledged.

00049, China; orcid.org/0000-0001-5148-762X ;

Email: zhugl@licp.cas.cn

Chun-Lin Lv − School of Pharmacy and Center on

Translational Neuroscience, Minzu University of China,

Beijing 100081, China; Email: chunlinlv@muc.edu.cn

Lin He − State Key Laboratory for Oxo Synthesis and Selective

Oxidation (OSSO), Suzhou Research Institute of LICP,

Lanzhou Institute of Chemical Physics (LICP), Chinese

Academy of Sciences (CAS), Lanzhou 730000, China;

University of Chinese Academy of Sciences, Beijing 100049,

China; Dalian National Laboratory for Clean Energy, CAS,

Dalian 116023, China; orcid.org/0000-0001-7437-

Notes

The authors declare no competing ﬁnancial interest.

ACKNOWLEDGMENTS

L.H. would like to thank the Dalian National Laboratory for

Clean Energy (DNL) Cooperation Fund and the CAS

■

(

DNL201919). This work was ﬁnancially supported by the

National Natural Science Foundation of China (nos.

1802151, 21972152, and 21802152) and the Natural Science

443; Email: helin@licp.cas.cn

Foundation of the Jiangsu Higher Education Institutions of

China (BK20180249). L.H. and G.Z. also acknowledge the

grant from the Key Research Program of Frontier Sciences of

CAS (QYZDJ-SSW-SLH051) and the Youth Innovation

Promotion Association of CAS (2018453).

Authors

Qiongyao Chen − State Key Laboratory for Oxo Synthesis

and Selective Oxidation (OSSO), Suzhou Research Institute

of LICP, Lanzhou Institute of Chemical Physics (LICP),

Chinese Academy of Sciences (CAS), Lanzhou 730000,

China; University of Chinese Academy of Sciences, Beijing

REFERENCES

■

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